Method of purifying hydrocarbon oils



AWR 299 194% H. mmans 5ML 292399859 METHOD 0F PURFYING HYQRCRBON @ELS Filed Aug. 16 1958 y g. f M ju /Q 4Patented pr. 2,

2,239,859 METHOD or rvnngc HYDnooAaoN Elmer H.

Records and JamesE. Louttit,

Tacoma, Wash.

Application August 1s, 193s, 'serial No. 225,142

. naphthalene so used iswiirst dissolved in benzol.

8' Claims.

This invention relates to a .process forrp'urifying hydrocarbon oils, such ascrude petroleum, cracked petroleum productsand residuum bottoms, and it is the principal object of this invention to provide a, simple process for treating such crude hydrocarbon oil whereby to so convert the forms of sulphur contained therein that they may be easily removed. More specically, the invention resides in .the process whereby the forms of sulphur are removed by washing with proper reagents, to leave a hydrocarbon oil that is substantially free of sulphur and` sulphur compounds; this process being applicable not only with crude hydrocarbon oils, but also with 'various forms of residuums from cracked petroleum oils and the various fractions distilled there- `from. n

This process is based upon the fact that many crude petroleum oils contain sulphur in various forms, which, if not removed, pass on into the l distillates `when the oil is treated, andthe fact that it is advantageous tbV remove `a`alarge portion of such sulphur compounds rofrn the crude `hydrocarbon before subsequent treatment for In thisrcase, the naphthaleneLbenzol solution is preferably added to the metallic salt solution and the dispersing agent. This isdone by delivering such solution from the tank 2| containing it through the pipe 22 'intothe' mixer l2.

The emul'siled mass of catalyst in the required amount is discharged from the storage tank 2i) through the pipe 40 into the charging stock tank 23. Into this same tank23 isv next delivered vthrough the pipe 24 therequired amountof the hydrocarbon oil to 4be treated or rened from the tank 25 containing it, and hydrocarbon oil and catalyst thoroughly mixed. This mass forms the charging stock for introduction in the reaction chamber to be stmseque'nthfy described.

. By reference to, the drawing `it VWill be `apparent 300 rb and 806 F., bringing about reactions form oi sulfonated oil such as sulionated castor. i

oil contained in receptacle I3 is delivered to the mixer i?! throughthe pipe i4. Intramine is the.

trade name for designating the compounds of 0,0 dithiobisanaline. When the salt and dispensing agent have been thoroughly mixed, water from the tank I5 heated to the desired temperature by means of heating 'jacket l5 is delivered to the mixer l2 through the. pipe i6 in an amount sufficient to dissolve the mixture of the salt and dispersing agent. A small quan-l tits' of the oil to be treated contained in .the tank i? is then delivered to the mixer l2' through the pipe I8 so as to thoroughly emulsify the mass. The emulsified mass oi catalyst is then discharged frcrn the mixer it! through the pipe i9 in the catalyst stcrage tank 2t.

With certain types of hydrocarbon oils we have found it advantageous to add. to the catalyst a determined amount ci crude naphthalene. The

immaginare is proviiedwinh a steam hearing Jacket 26 for l thepurpose of preheating the oil, ifdesired,

Y The advantag ofdourr method oi preparing the Vcatalyst and hydrocarbon bil is'tlat complete dispersion oi the catalyst in the crude oil brought about, and under the subsequent heat treatment, decomposition of the sulfur compounds is accelerated.

The mixture of catalyst and hydrocarbon oil is introduced into the reaction chamber 21 from the charging stock tank 23 through the pipe 28 wherein it is heated to a temperature of Vbetween cooler 33 wherein it is cooled. Ilromthe cooler' 33 .the treated mass is dischargedthrough the pipe 34 into a washing tank 35 wherein it is subjected to a Washing with water to remove the suliur compounds decomposed by the reactions' of our process and the catalyst remaining there# in. The water for use in the tank 35 is delivered u from the Water .tank 36 through the pipe 3l. After completion of the washing, the refined cil is delivered through the pipe 3E into the refined oil storage tank es.

space provided adjacent thereto. is of the approximate relation of one to ve.

In the operation of our method it is also desirable to preheat the hydrocarbon oil slightly by some form of heat exchanger, and charging the preheated mixture of hydrocarbon oil and catalystdirect to the reaction retort. It is not compulsory, however, that heating prior to mixture with the catalyst be adopted to bring about the purification of the hydrocarbon oil under our method, as the method we use of emulsifying oil and catalyst can be begun with oil at normal temperatures.

Prompt removal of the heat treated hydrocar bon oil from the reaction chamber and rapid cooling thereof has been found to be advantageous to our method.

The type of reaction vessel or chamber rethereof in which there can be inserted electric heating elements of the insert type is also applicable. Although we prefer the above types of reaction retorts our invention is applicable to various other forms of heating furnaces, wherein hydrocarbon oils may be enclosed for the proper heating thereof.

A distinct advantage of our method is -that no carbon is deposited in the reaction chamber and the amount of gases formed are very slight.

We have found through repeated tests and experimentation that our method is applicable to hydrocarbon oils containing variable percentages of total sulfur.

The time required to bring about the reactions desired from the heating of the oil and catalyst is dependent upon the type of hydrocarbon oil under treatment. It is desired to heat to required temperature as rapidly as possible.

The term hydrocarbon oil as used herein includes all hydrocarbon oils of mineral origin.

Having thus described our invention, what we claim as new therein and desire to secure ny Letters Patent is 1. The method of rening hydrocarbon oils containing sulfur compounds which comprises treating said hydrocarbon oil with a catalyst including a metal salt selected from the group consisting of ferric chloride, aluminum chloride, and a dispersing agent consisting of sulfonated castor oil, at an elevated temperature to convert the sulfur compounds into soluble form.

,2. The method of rening hydrocarbon oils containing sulfur compounds which comprises 3. The method of rening hydrocarbon oils containing sulfur 'compounds which comprises treating said hydrocarbon oil with a catalyst including naphthalene, a metal salt selected from the group consisting of ferric chloride, aluminum chloride, and a dispersingl agent consisting of sulfonated castor oil at an elevated temperature to convert the sulfur compounds into soluble form. l

4. The method of refining hydrocarbon oils containing sulfur compounds which comprises treating said hydrocarbon oil with a catalyst includngnaphthalene, a metal salt selected from the group consisting of ferrie chloride. aluminum chloride, and a dispersing agent consisting of sulfonated castor oil, at a temperature between 300 F. and 800 F.

5. The method of refining hydrocarbon oils containing sulfur compounds which comprises treating said hydrocarbon oil with a catalyst including a metal salt selected from` the group consisting'of ferric chloride, aluminum chloride. and a dispersing agentV consisting of sulfonated castor oil, at an elevated temperature to convert the sulfur compounds into soluble form, and washing the thus treated oil to remove the sulfur soluble compounds therefrom. Y v

6. The method of refining hydrocarbon oils containing ,sulfur compounds which comprises treating said hydrocarbon oil with a catalyst including a metal salt selected from the group consisting of ferric chloride, aluminum chloride, and a dispersing agent consisting of sulfonated castor oil, at a temperature between300F. and 800 F. to convert the sulfur compounds` into soluble form, and treating the thus treated oil with water to remove the sulfur soluble compounds therefrom. Y v

7. The method of refining hydrocarbon oils containing sulfur compounds which comprises treating said hydrocarbon oil with a catalyst including a metal salt selected from the group consisting of .ferric chloride, aluminum chloride, and a dispersing agent consisting of sulfonated castor oil, at a temperature between 300 F. and V800 F. to convert the sulfur compounds into soluble form, cooling the .thus treated oil, and Washing the cooled treated oil with water toremove the ELMER H. RECORDS. JAMES E. LOU'I'IIT. 

